The chemical modification of polymers is a commonly known means of altering and optimizing the physical and mechanical properties of such compounds. Chemical reactions on unsaturated polymers are of particular interest because of the technological importance of the parent materials and the reactivity of the available double bonds. Addition reactions to the olefinic bonds of polymers are well known in the art.
U.S. Pat. No. 4,704,427 of Kitahara et al., issued Nov. 3, 1987, discloses that a polymer or copolymer containing --C(CH.sub.3).dbd.C-- bonds can be modified by reaction using a Lewis acid catalyst and a co-catalytic amount of a cationic polymerization catalyst having active hydrogen or halogen. The cationic polymerization catalysts include trichloroacetic acid, tribromoacetic acid, water plus methyl alcohol, 2,4-dinitrophenol, p-nitrophenol, t-butylchloride, triphenylmethane chloride or benzyl chloride. The preparation of an adduct is not disclosed.
U.S. Pat. No. 3,523,108 of Boutsicaris et al., issued Aug. 4, 1970, discloses a process for esterifying polymers having repeating units derived from butadiene by reaction with a mixture of sulfuric acid with saturated aliphatic or aromatic carboxylic acid. The reaction involves the addition of acetic acid to a double bond of the polymer to form pendant acetate ester groups.
U.S. Pat. No. 3,595,851 of Boutsicaris et al., issued Jul. 27, 1971, discloses the peroxide curing of hydroxy and acyloxy derivatives of butadiene liquid polymers.
Japan 54-60525 of Ikeda, published Nov. 28, 1980, discloses a method for preparation of aromatic ether derivatives of unsaturated polymers by reacting aromatic hydroxy compounds or naphthols with the unsaturated polymer in the presence of a catalyst. Also disclosed is an addition product of a phenol with polydienes, but it is taught that isoprene homopolymers do not react.
All of the above disclose modification reactions involving use of a suitable catalyst. None teach the direct addition of halogenated carboxylic acids to olefinic polymers.
T. C. Chung disclosed at J. Polym. Science: Part A 27, 3251 (1989), preparation of diblock copolymers containing butadiene or isoprene and hydroxyl ethyl vinyl moiety. These polymers were prepared from polydiene by hydroboration followed by oxidation. The hydroxyl group of these polymers is all primary hydroxyl group.
It is therefore an object of the present invention to provide a process for the direct addition without use of a catalyst of halogenated carboxylic acids to the unsaturated bonds of olefinic polymers.
It is a further object of the present invention to provide novel polymer adducts resulting from this addition reaction.
It is a further object of the present invention to provide novel polymers resulting from the saponification of the addition reaction polymer adducts.
It is also an object of the present invention to provide block or random copolymers incorporating the above novel products of the addition or saponification reactions.